Synthesis of quarternary melanin compounds and their use as hair dyes or for skin treatment

ABSTRACT

Water soluble, cationic products useful as hair colorants or for the treatment of skin which are esters or amides formed by reaction of melanin and a quaternary salt containing a reactive amino or hydroxyl group, as well as compositions containing them and methods of using such products to color hair or treat skin are described.

This application is a continuation-in-part of patent application U.S.Ser. No. 08/568,057, filed Dec. 6, 1995, now U.S. Pat. No. 5,686,084.

RELATED APPLICATIONS

Attention is directed to and concurrently filed patent application U.S.Ser. No. 08/568,056, filed 6 Dec. 1995 (Atty. Dkt. No. CP-1141), nowU.S. Pat. No. 5,702,712, which describes melanin reaction productshaving properties similar to those of the products of this invention,but which are prepared from different starting materials.

BACKGROUND OF THE INVENTION

This invention relates to water soluble reaction products prepared bythe oxidative polymerization of quaternized5,6-dihydroxyindole-2-carboxylic acid amides or esters, to compositionscontaining such products, to methods of coloring hair or treating skinutilizing the compositions and to kits containing the compositions. Morespecifically, the invention relates to reaction products characterizedby a quaternary nitrogen substituent and to intermediates useful for thepreparation of the reaction products.

The reaction products of this invention are mixtures of many compoundsformed by the oxidative polymerization of the aforementioned amide orester derivatives of 5,6-dihydroxyindole-2-carboxylic acid (DHICA). Theoxidative polymerization of DHICA and certain of its selectedderivatives is described in commonly owned U.S. Pat. No. 5,346,509, thedisclosure of which is incorporated herein by reference. The particularDHICA derivatives which are oxidatively polymerized to form the productsof this invention are neither described nor suggested in the '509patent.

To facilitate understanding of this invention, the following system willbe employed in its description:

A: The oxidative polymerization products should be understood to be thereaction products of the invention. In addition to the term "reactionproducts of the invention", they are sometimes referred to as haircolorants, hair dyes or skin treatment products and, often, melanin likeproducts of the invention.

B: The quaternized products formed by reaction of DHICA with selectedquaternary compounds to be described more fully hereinafter are referredto as "intermediates" or as "intermediates of the invention".

C: Compositions of the invention may take several forms depending ontheir intended use. If the products of the invention are to be directlyadded to the hair of it they are to be formed on the hair by oxidativepolymerization of intermediates of the invention, they will be aqueous.If they are to be employed for skin care they may be aqueous,non-aqueous or they may be mixtures of polar or non-polar organicsolvents and may be either free flowing or viscous.

Notwithstanding their melanin-like properties, the reaction products ofthis invention are not true melanin derivatives. The reaction productsof the present invention are mixtures of many compounds and thus cannotbe precisely defined by a chemical formula. Accordingly they will bedefined herein by their method of preparation. It is believed that themixture of the compounds comprising the reaction products of thisinvention includes some dimers, trimers and tetramers of theintermediates. However, most species are oligomers and many are probablytrue polymers. Surprisingly, they have substantially similar haircoloring and other properties compared to the melanin derivativesdescribed in U.S. Ser. No. 08/568,056 (CP1141).

Naturally-occurring melanin is the pigment that gives hair its color. Ageneral discussion of the properties and chemistry of melanins may befound in Prota, G., "Progress In The Chemistry of Melanins And RelatedMetabolites," Mcd. Res. Reviews, 8:525-56 (1988) and Moncrieff, R. W.,Manufacturing Chemist, XXI, 8, 330-34 (August 1950). The gradualreduction of melanin formation with age causes hair to become gray.

Naturally-occurring melanin pigment itself is unacceptable for use in ahair dye composition because it is easily removed by rinsing or rubbingand leaves the hair feeling rough. One present method for coloring grayhair involves the use of naturally-occurring melanin precursors such asDHI that when combined with an oxidant, form useful melanin likepigments. See, for example, U.S. Pat. No. 3,194,734 (Seemuller et al.),U.S. Pat. No. 4,808,190 (Grollier et al.), and U.S. Pat. No. 4,888,027(Grollier et al.). See also U.S. Pat. No. 5,346,509 (Schultz et al)which describes the conversion of DHICA to melanin like pigments.

The primary disadvantage is that the hair colors initially produced withmelanin precursor dyes are undesirable achromatic colors (cold grays andblacks). Hair dyed with these colorants must undergo a second treatmentstep with an oxidant such as hydrogen peroxide to achieve naturalchromatic colors (warm yellows, reds, and browns). See, for example,U.S. Pat. No. 3,194,734 (Seemuller et al.). In addition, melaninprecursors are expensive and, because they are highly reactive, aredifficult to work with. The use of melanin precursors also can result inundesirable scalp and skin staining.

Furthermore, because the pigments are formed from the melanin precursorsin the hair shaft, the hair colors produced using the melanin precursorsare permanent. The hair color must grow out to return to its originalcolor. Often, consumers prefer to use a temporary hair color that willwash out after one or two shampoos.

The compositions described in PCT patent application S.N. US93/11174filed Nov. 17, 1993 are useful as temporary hair colorants. Thesecompositions contain melanin derivatives prepared by forming a complexbetween a water soluble anionic melanin with selected quaternarycompounds, suitably alkyltrimonium halides, alkylalkonium halides ordialkyldimonium halides such as cetrimonium halide or stearalkoniumhalides. These complexes impart a temporary coloring to human hair whendeposited thereon in aqueous compositions and thereafter dried. Althoughsuch compositions are acceptable to many consumers, they may not beacceptable to others because they wash off the hair too readily. Onlyrarely do they survive a single shampoo. In fact, normally they requirea "leave on" treatment since they may be readily removed with even awater rinse.

The art has sought hair coloring compositions providing colors that arenot as difficult to use as the melanin precursors or as permanent dyes,but are more permanent than the colors provided by the above describedtemporary hair colorants, i.e. dyes which will survive 4 to 6 shampoosor can be mixed with additional dyes in a shampoo base in order tofreshen temporary hair colors. The hair colorants utilized in thecompositions of this invention have these desirable properties. In thatrespect they are similar to the products of the above identified U.S.Ser. No. 08/568,056 (CP-1141), but are prepared differently.

The compositions of this invention produce in a single treatment stepsemi-permanent natural-looking hair color that resist fading insunlight, resist rub off and resist bleeding in contact with water. Thecompositions are inexpensive and simple to work with. It hassurprisingly been found that aqueous compositions containing thereaction products of this invention will, when applied to hair, impart asemi-permanent color to the hair which will survive more than threeshampoos without substantial loss of color characteristics. A particularadvantage of the reaction products of this invention is that they can becombined with other hair colorants in a shampoo base to freshen theexisting hair color whereby the hair color is renewed and retained foran appreciably further period of time. Another is that the reactionproducts can be used for simultaneous coloring and conditioning of hair.

The products of this invention are also useful for skin care. They maybe used alone or, preferably, in conventional skin care compositions.When so employed, they function both as skin colorants to impart atanned appearance to the treated skin and as sun screen agents toprotect the skin from harmful infrared rays.

With both skin and hair, the products exhibit the other attributes ofnatural melanin, i.e., they are antioxidants and free radical scavengersand minimize hair damage caused by oxidants and free radicals oftenpresent in the hair after atmospheric exposure.

U.S. Pat. No. 5,006,331 (Gaskin) discloses the use of melanincompositions containing triethanolamine and ferric chloride. Theresultant mixture of melanin, triethanolamine and ferric chloride issaid to be useful for skin protection, for wound healing and forstrengthening hair. An alternate composition contains trypsin in analkaline medium. Melanin is present in the skin protectant compositionsof Gaskin in an amount of from about 0.001 to about 0.09%, along withfrom about 0.0001% to about 0.27% ferric chloride, both being on aweight basis based on total weight. The skin protectant compositionfurther contains up to about 5% by weight triethanolamine. While notproviding a range of concentration for the amount of melanin hydrolysatefor the hair protectant compositions according to her invention, Gaskinstates at column 6, line 30 that it is present therein in an amount ofonly about 0.0015% by weight of the total composition. However, thislevel of Gaskin's melanin hydrolysate is wholly insufficient to impart acolor to hair. Moreover, neither of Gaskin's methods provide a melaninmaterial of a cationic character.

PCT Application WO 91/17738 discloses the use of soluble melaninderivatives in a process for producing lightly colored melanins that areaesthetically suitable for use in cosmetic compositions.

WO 94/25532 describes melanin linked to a lipid to form a lipomelaninand its use in a sunscreen product.

It is an object of this invention to provide an aqueous composition forsemi-permanently coloring hair using water soluble melanin like productsof the invention.

It is also an object of this invention to provide compositions that willproduce a semi-permanent natural-looking hair color that resists fadingin sunlight, will not rub off, and will not bleed when in contact withwater.

It is further an object of this invention to provide inexpensivecompositions for semi-permanently coloring hair using water solublemelanin like products of the invention.

It is also an object of this invention to provide compositions that aresimple to work with for semi-permanently coloring hair using watersoluble melanin like products of the invention.

It is also an object of this invention to provide a one-step process forsemi-permanently coloring hair.

It is a further object of this invention to provide a compositions forsimultaneously coloring and conditioning hair.

It is a still further object of this invention to provide compositionswhich when used with appropriate shampoos are useful for freshening haircolors.

It is a still further object of this invention to provide novel melaninlike products of the invention and compositions thereof for skin care.

It is a still further object of this invention to provide novelintermediates useful for the production of melanin like products of theinvention.

SUMMARY OF THE INVENTION

The presently preferred products of the invention are quaternarysubstituted esters or amides which may be obtained by oxidativepolymerization of a novel intermediate of the invention represented bythe formula: ##STR1## wherein: Y is --O-- or ##STR2## R is hydrogen or asubstituent that is chemically non reactive in the polymerizationreaction, typically an alkyl containing from about 1 to about 6 carbonatoms, and preferably methyl or ethyl.

R₁ , R₂ and R₃ are groups that in combination one with the other andwith R₄ quaternize the nitrogen to which they and R₄ are bonded,

R₄ is a linking group as defined below, and

X is an anion.

The intermediates of this invention as will be recognized from the aboveformula are quaternary substituted esters or amides obtained by reactingDHICA or its N-substituted derivatives with a quaternary ammonium salt,N⁶¹ R₄ (YH)R₁ R₂ R₃ X⁻. R₁,R₂,R₃ and R₄ (YH) maybe any chemical groupsuitable to quaternize the nitrogen to which they are bonded, and thatdoes not prevent ester or amide formation when the DHICA species and thequaternary salt are reacted. The quaternized melanin amide or esterprecursor compounds (I) of the invention may be prepared from any of awide variety of quaternary compounds that react with DHICA or itsN-substiuted derivatives. The quaternized melanins of this invention areobtained by oxidative polymerization of the intermediate compound (I),and have cations that interact with hair and become attached to the hairby a cation/anion attraction of the cation for the anionic hair. It isthis electronic attraction of the cation of the quaternary compound forthe anionic charge of the hair which renders the hair colorants of thisinvention semipermanent rather than temporary as are the hair dyes ofthe above cited PCT patent application S.N. US93/11174 filed Nov. 17,1993.

Suitably, R₄ may be an unsubstituted or substituted alkylene grouphaving from 1 to 20 carbons, preferably a straight chain unsubstitutedalkylene group having 6 to 15 carbons, and R₁, R₂ or R₃ may be anunsubstituted or substituted alkyl group having from 1 to 22 carbons,preferably one of R₁, R₂ or R₃ having from 12 to 16 carbons and two ofR₁, R₂ or R₃ having from 1 to 6 carbons. The alkylene and alkyl groupsare preferably straight chained. Suitable substituent groups present inR₄, R₁, R₂ and R₃ may be hydroxy; mono- or polyhydroxyalkyl andalkyloxy, mono- or polyhydroxyalkyloxy, the alkyl group having from 1 to6 carbons, preferably 1 to 4 carbons, especially 1 to 2 carbons, withtypically up to about 3 hydroxy groups; amino and alkylamino with up toabout 6 carbons, preferably 1 to 3 carbons; halo; cyano, and nitro. R₄,R₁, R₂ and R₃ may also be an unsubstituted or substituted alkylamidogroup having 1 to 6 carbons, preferably 1 to 3 carbons; an alkylene ordialkylene substituted alicyclic or aryl group, especially phenyl butalso cyclohexenyl and naphthyl, the alkylene group(s) having from 1 to 6carbons, or a heterocyclic such as pyrolle, morpholinyl or piperidinyl.Any of the aryl, alicyclic or heterocyclic groups may be furthersubstituted as set forth above with respect to the alkyl (or alkylene)group. The selection of a substituent group is limited only with regardto whether ester or amide formation would be compromised, and whetherthe reaction product of the DHICA species and quaternary is sufficientlysoluble to permit formulation in an aqueous-based hair dye product. Thesubstituent groups should not impart instability to the molecule in viewof steric hinderance or otherwise.

As previously mentioned the quaternary reactant has at least one aminoor hydroxy group YH associated with R₄ that is available to form anamide or ester compound in accordance with this invention. However, R₄may have two or more reactive hydroxy or amino groups associated withit. Similarly, any of R₁, R₂ and R₃ may also have one or more additionalhydroxy or amino groups. When multiple reaction sites are available foramide or ester formation, the reaction will take place at one of them.The other substituents present on R₄, R₁, R₂ and R₃ of the quaternaryreactant are chemically compatible with respect to ester or amideformation but may be further reacted to produce desired colors.

The above identified products are especially preferred when they areprepared from quaternary compounds containing an unsubstitutedaminoalkylene or hydroxyalkylene group together with at least one otherlong chain alkyl group attached to the positively charged nitrogen. Themost preferred products of the invention are those which contain atleast one long chain alkyl group and at least one short chain alkylgroup containing from about 1 to 6 carbon atoms, suitably methyl orethyl. Although the invention contemplates products in which all of theR₄ groups are long chain, these are not preferred because they aredifficult to prepare due, principally, to steric hindrance.

Suitable quaternary materials that may be used in the practice of thisinvention are set forth, generally, in the CTFA Cosmetic IngredientHandbook (1st Ed., 1988) at pages 40-42 (quaternary ammonium compounds).The entire disclosure of this citation is incorporated herein byreference. Suitability of specific compounds may be determined by one ofordinary skill in the hair dye art by simple experimentation. They arecompounds which will react with DHICA to produce internediates which canbe oxidatively polymerized to form the positively charged products ofthe invention having at least one counterion which is an anionic moiety,e.g., a halide or methosulfate. Using the nomenclature of the CTFAHandbook, which is widely used and accepted by chemists in the cosmeticart, illustrative cationic materials are hydroxy or amino substitutedalkyl trimonium halides, alkylalkonium halides and the dialkyldimoniumhalides, wherein the alkyl groups have about 1 to about 22 carbons andthe halide is Cl or Br. Useful quaternium compounds include for example,the quaternium series of compounds such as Quaternium 16, 22, 30, 36,46, 78, 79, 80 and 82. Other suitable quaternary reactants will bereadily apparent to the skilled artisan after the benefit of thisdisclosure.

It will be apparent from the foregoing that the quaternary compoundsused to produce intermediates may contain a variety of functional groupsboth in the main chain or attached thereto.

The anion in the intermediates of this invention may be any of thosenormally associated with quaternary compounds. Typically they arehalides, preferably chlorides or bromides.

DETAILED DESCRIPTION OF THE INVENTION

The intermediates of the invention may be formed by any of the usualmethods of forming amides or esters.

For example, to form amides, DHICA may be reacted with an aminoalkylsubstituted quaternary compound in an aqueous buffer at a pH of about 7at ambient temperature in the presence of a carbodiimide such as1-ethyl-1,3-(3-dimethylaminopropyl) carbodiimide.

Esters may be prepared for example, by reacting equimolar quantities ofthe reactants in an aqueous buffer at pH 7.

The intermediates of this invention may be oxidatively polymerized by anumber of procedures known to those skilled in the art. The melanin likeproducts of the invention may be produced by treatment of the selectedintermediate with an oxidizing agent such as, for example, hydrogenperoxide, potassium ferricyanide, potassium permanganate or ammoniumpersulfate. These procedures are well known and are described forexample in U.S. Pat. Nos. 5,173,083; 5,346,509; 5,273,550 and 4,804,385,the entire disclosures of which are incorporated herein by reference.

The amount of quaternized melanin like hair colorant required in theaqueous hair dye compositions of this invention whether the haircolorant is preformed or formed on the hair will vary according tofactors such as the carrier used, the initial hair color of the userprior to dyeing, the desired end hair color and other factors well knownto those skilled in the art. A tinctorially effective amount of haircolorant should be used. In general, the amount required is at leastabout 0.1%, typically from about 0.1% up to its solubility limit in thecomposition, but generally up to about 5.0%, and preferably from about0.2% to about 3.0%, all concentrations being on a weight basis based onthe total weight of the composition.

Skin compositions employing the products of this invention are generallyless concentrated than those used as hair colorants. Typically, theywill contain from about 0.01% to 10%, preferably 0.05% to 1% of at leastone product of the invention dissolved, emulsified or suspended in apharmaceutically acceptable skin vehicle which may be aqueous ornon-aqueous and may comprise water, inert oils, emollients, surfactants,buffers or other additives such as those illustrated in the examples.

Although the pH of the aqueous compositions of this invention may not beso low or high as to damage skin or hair, the compositions are useful ata wide range of pH values. The optimal pH for a particular compositionmay vary with the hair colorant employed. In general, however, the pH ofthe composition will be about 3 to about 10, preferably 5 to 10.

In addition to the selected hair colorant or mixture of hair colorantsof the invention, it may be desirable to include cosmetically acceptablecarriers in the hair colorant compositions of this invention. Acceptablecarriers vary from simple solutions or dispersions with aqueous oralcoholic solvents to complex mixtures that contain thickening or otheragents. The carriers that may be used in accordance with this inventionmust be compatible with the selected dye.

It may also be desirable to include in the compositions of thisinvention adjuvants or additives that are commonly found in suchcompositions, in amounts effective to provide their intended function.Such adjuvants or additives include, for example, solvents, solubilizingagents, surfactants, thickening agents, alkalizing agents, chelatingagents, preservatives and fragrances.

The solvents that may be used include organic solvents or solventsystems that are compatible with the other components. A number oforganic solvents are known in the art that are useful for such purposes.These organic solvents include alcohols, particularly alkyl alcohols of1-6 carbons, especially ethanol and propanol; and glycols of up to about10 carbons, especially diethyleneglycol; monobutyl ether; carbitols andbenzyl alcohol.

The thickening agents that may be used include, polyvinylpyrrolidone,gum arabic, cellulose derivatives such as methylcellulose orhydroxyethylcellulose, and inorganic thickeners such as bentonite. Thesolubilizing agents that may be employed include for example,ethoxylated fatty alcohols. The preservatives that may be used include:methyl and propyl paraben, 2-phenoxyethanol, DMDMH, and Kathon CG.

A special advantage of the hair colorants of this invention is thatcertain of them can be employed to both color and condition the hair atthe same time. It is known that when long chain alkyl substituentscontaining certain quaternary ammonium salts are deposited on humanhair, they improve combability, i.e., the relative ease with which haircan be combed, by imparting a certain lubricity to the hair as well asby providing an antistatic effect. Both of these effects combine to makethe hair easier to manage so that the desired appearance of the hair canbe more readily achieved. Compositions having these properties arecalled "hair conditioners". See, for example, A. C. Lunn and R. E.Evans, The Electrostatic Properties of Human Hair, J. Soc. Cosmet,Chem., 28, 549 (1977).

Products of this invention formed by oxidative polymerization ofintermediates having one substituted or unsubstituted alkyl groupscontaining from about 12 to about 16 carbon atoms are preferred for bothcolorant and conditioning properties. Quaternary reactants useful forsuch concurrent activity include, for example, several of the Quaterniumcompounds mentioned above.

In another preferred aspect of the invention, the water soluble productsof the invention are incorporated into a shampoo base which alsocontains auxiliary hair colorants to effect simultaneous coloring andcleaning of the hair. This feature of the invention is especially usefulto freshen the color of previously dyed hair.

Shampoos are well known to those skilled in the art and need not bedescribed with any particularity. In general, they are aqueous solutionscontaining from about 1% to about 50% by weight of a surfactant whichmay be cationic, anionic, non-ionic or amphoteric. Suitable surfactantsinclude for example, behenealkonium chloride, dodecyldimonium chloride,sodium lauryl sulfate, sodium laureth sulfate, cocamidopropyl betaineand cocamidopropyl sultaine. Other useful surfactants may be identifiedby resort to McCutcheon's Emulsifiers and Detergents (North Amer.Edition 1987) which is incorporated herein by reference. In thecompositions of this invention, the amount of surfactant is about thesame as employed in conventional shampoos.

It will be appreciated that none of the various additives describedabove can be employed in the hair colorant compositions of the inventionif they insolubilize the hair colorants of the invention at anyconcentration.

A further aspect of the present invention is the optional incorporationof one or more known hair color modifiers in the hair colorantcompositions of the invention. These include for example, direct dyes,primary intermediates and couplers.

The concentration of hair color modifier is normally less than about 10mg/ml, and preferably is present in the reaction medium at from about0.01 to about 5 mg/ml, most preferably from about 0.05 to about 2 mg/ml.The amount of these components should not be so great as to causeprecipitation of the hair colorants of the invention.

A wide variety of direct dyes, primary intermediates and couplers areknown to the skilled artisan and can be employed in this invention.

The presently preferred primary intermediates and couplers with whichthey will react include:

Primary Intermediates:

p-phenylenediamine

p-aminophenol

o-aminophenol

N,N-bis(2-hydroxyethyl)-p-phenylenediamine

2,5-diaminopyridine

p-toluenediamine

Couplers:

resorcinol

m-aminophenol

α-naphthol

5-amino-o-cresol

2-methylresorcinol

4,6-di(hydroxyethoxy)-m-phenylenediamine

m-phenylenediamine

Suitable direct dyes include, for example nitro dyes, azo dyes andanthraquinone dyes.

This invention also provides a process for coloring hair, whichcomprises applying to the hair an aqueous composition comprising aproduct of the invention. The compositions may be applied to the hair byconventional techniques known in the art. For example, they can bepoured over the hair or applied with an applicator. The amount of timefor which the dye composition must be in contact with the hair is notcritical. It may vary from about 2 minutes to about one hour, but isusually from about 5 minutes to about 30 minutes.

While the presently preferred method of utilizing the products of theinvention as hair colorants is to apply the preformed oxidativelypolymerized melanin like products directly to the hair in aqueouscompositions, it is also possible to achieve hair coloration or to treatskin by mixing an oxidant with an intermediate of the invention justprior to application or during application so that a product of theinvention is formed an the hair or skin.

The invention also includes kits containing a composition of thisinvention. A kit may comprise one container which contains a compositionincluding all of the various components described above. Alternatively,there may be two or more containers each containing separate componentswhich are mixed on the hair or just prior to application to the hair orskin, or after application thereto.

The hair coloring effects achieved with the products of this inventionmay be evaluated utilizing the standard Hunter Tristimulus values. Inthe Hunter method, the parameters a and b may be positive or negativeand define the chromatic condition of the hair. Thus, the more positivethe a value, the greater the redness of the hair, while a negative avalue indicates greeness. Similarly, positive b values indicateyellowness, while negative b values indicate blueness. The L parameteris a measure of color intensity, and has a value of 0 for absolute blackto 100 for absolute white.

The following non-limiting examples are given by way of illustrationonly. In the examples, the formation of a cationic, positively chargedpigment was shown by electrophoretic measurements in 0.05M sodium boratebuffer, pH 9 at 250 Volts.

EXAMPLES

Abbreviations used: MES buffer is morpholinoethylsulphonate. EDC is1-ethyl-3-(3-dimethylaminopropyl)carbodiimide. DHICA is5,6-dihydroxyindole-2-carboxylic acid.

Example 1

REACTION PRODUCT OF OXIDATIVELY POLYMERIZED DHICA-QUATERNIUM 22

A solution of DHICA (200 mg) in nitrogen flushed 0.1M MES buffer, pH 7(40 ml) is treated with 1.74 ml of Quaternium 22, maintaining pH atabout 7. A few mg of sodium dithionite are added, followed by 150 mg ofEDC under nitrogen. After 1 h, an additional 150 mg portion of EDC isadded, and the resultant mixture is left at room temperature understirring and under nitrogen until almost all the DHICA has been consumed(about 20 h). The crude mixture is then treated with potassiumferricyanide (1 g) in 0.1M phosphate buffer (20 ml) at room temperaturewith continuing stirring. After 1.5 h, the solution is dialyzed againstwater over at least 10 h. The pigment which separates is collected bycentrifugation and washed with water.

Example 2

A 1% solution of the product of Example 1 in pH 10 buffer was preparedand applied to bleached hair for 15 minutes. Afterwards, the hair wasrinsed with water and dried.

    ______________________________________                                        Hunter       L            a     b                                             ______________________________________                                        before treatment                                                                           66.4         1.4   18.7                                          after treatment                                                                            42.7         3.2   14.5                                          ______________________________________                                    

A noticeable color and conditioning effect is imparted to the hair. Thehair was shampooed, rinsed and dried. A significant amount of haircolorant remained on the hair.

    ______________________________________                                        Hunter       L            a     b                                             ______________________________________                                        shampooed hair                                                                             51.7         2.0   16.2                                          ______________________________________                                    

Example 3

A skin care composition is prepared by thoroughly mixing the followingcomponents:

    ______________________________________                                        Product of Example 1                                                                           0.1%                                                         Methyl cellulose 0.5%                                                         Glycerin         2.0%                                                         Ethanol          11.0%                                                        Water            85.5%                                                        Fragrance        Q.S. 100%                                                    ______________________________________                                    

When applied to the skin, the composition imparted a darker color.

Example 4

DHICA (1.5 g) is dissolved in DMF (4 ml) and is treated with a solutionof 2-aminoethyltrimethyl ammonium chloride (4 g) in water (3 ml)followed by EDC (5.45 g) solubilized in a mixture of water (2 ml) andDMF (4.5 ml). After about 1 h, 3 g of EDC is added and the mixture isstirred for additional 45 min. Sodium periodate (2 g) in water (12 ml)is then added and the mixture is allowed to stand under stirring for 20min. Oxidation is eventually stopped with a small amount of sodiumbisulfite and the resulting pigment is dialyzed against water andlyophilized.

Example 5

A sunscreen composition is prepared by thoroughly mixing the followingcomponents:

    ______________________________________                                        Product of Example 1                                                                              0.1                                                       Ethyl dihydroxypropyl PABA                                                                        2.0                                                       Propylene Glycol    20.0                                                      Oleth-20            4.7                                                       Laneth-16           4.7                                                       Water               68.5                                                      ______________________________________                                    

When applied to the skin the composition afforded protection against sunrays.

What is claimed is:
 1. A water soluble cationic polymer obtained byoxidative polymerization of a 5,6-dihydroxyindole carboxylic acid esteror amide of the formula: ##STR3## wherein: Y is --O-- or ##STR4## R ishydrogen or a chemically nonreactive substituent, R₁, R₂, R₃ and R₄ aregroups that in combination one with the other quaternize the nitrogen towhich they are bonded, andX is an anion.
 2. The polymer of claim 1 inwhich:R is hydrogen or an alkyl of from 1 to 6 carbons; R₁, R₂ and R₃,which may be the same or different, are alkyls of from 1 to 22 carbons,an amidoalkyl group, the alkyl having from 1 to 6 carbons; an alkyl- ordialkyl-substituted aryl or alicyclic group, the alkyl group(s) havingfrom 1 to 6 carbons or a heterocyclic group selected from morpholinyl,piperidinyl or pyrrole, or R₄ is alkylene group of from 1 to 20 carbons;an amidoalkyl group, the alkyl having from 1 to 6 carbons; an alkylene-or dialkylene-substituted aryl or alicyclic group, the alkylene group(s)having from 1 to 6 carbons, or a heterocyclic group selected frommorpholinyl, piperidinyl or pyrrole, each group R₄, R₁, R₂ and R₃ beingunsubstituted or substituted with a substituent that does not preventester or amide formation, the substituents being selected from thegroups consisting of hydroxy; mono- and polyhydroxyalkyl having from 1to 4 carbons and from 1 to 3 hydroxy groups; alkloxy, mono- andpolyhydroxyalkyloxy having from 1 to 4 carbons and from 0 to 3 hydroxygroups; amino and alkylamino having from 1 to 6 carbons in the alkylgroup; amidoalkyl having from 1 to 6 carbons; halo; cyano, and nitro. 3.The polymer of claim 2 wherein R₄ is an alkylene and has from 6 to 15carbons; at least two of R₁, R₂ or R₃ are alkyl having from 1 to 6carbons, not more than two of R₁, R₂ and R₃ being substituted with agroup selected from hydroxy; mono- or polyhydroxyalkyl having from 1 to4 carbons and from 1 to 3 hydroxy groups; alkloxy, mono- orpolyhydroxyalkyloxy having from 1 to 4 carbons and from 0 to 3 hydroxygroups; amino or alkylamino having from 1 to 3 carbons in the alkylgroup; amidoalkyl having from 1 to 3 carbons; halo; cyano, or nitro, andR is hydrogen, methyl or ethyl.
 4. The compound of claim 2 wherein R ishydrogen; R₄, is alkylene or amidoalkyl, and R₁, R₂, and R₃ are alkyl ormonohydroxyalkyl.
 5. A composition comprising in an amount effective tocolor hair or treat skin, a polymer obtained by oxidative polymerizationof a quaternized indole of the formula: ##STR5## wherein: Y is --O-- or##STR6## R is hydrogen or a chemically nonreactive substituent, R₁, R₂,R₃ and R₄ are groups that in combination one with the other quaternizethe nitrogen to which they and R are bonded, andX is an anion, and acosmetically acceptable vehicle.
 6. The composition of claim 5 inwhich:R is hydrogen or an alkyl having 1 to 6 carbons, R₄ is alkylenegroup of from 1 to 20 carbons; an amidoalkyl group, the alkyl havingfrom 1 to 6 carbons; an alkylene- or dialkylene-substituted aryl oralicyclic group, the alkylene group(s) having from 1 to 6 carbons, or aheterocyclic group selected from morpholinyl, piperidinyl and pyrrole,or R₁, R₂ and R₃, which may be the same or different, are alkyls of from1 to 22 carbons, an alkylamido group, the alkyl having from 1 to 6carbons; an alkyl- or dialkyl-substituted aryl or alicyclic group, thealkyl group(s) having from 1 to 6 carbons or a heterocyclic groupselected from morpholinyl, piperidinyl or pyrrole, each group R₁, R₂,R₃, and R₄ being unsubstituted or substituted with a substituent thatdoes not prevent ester or amide formation, the substituent beingselected from the group consisting of hydroxy; mono- andpolyhydroxyalkyl having from 1 to 6 carbons and from 1 to 3 hydroxygroups; alkloxy, mono- and polyhydroxyalkyloxy having from 1 to 6carbons and from 0 to 3 hydroxy groups; amino and alkylamino having from1 to 6 carbons in the alkyl group; amidoalkyl having from 1 to 6carbons; halo; cyano, and nitro.
 7. The composition of claim 6 whereinR₄ is an alkylene and has from 6 to 15 carbons; at least two of R₁, R₂or R₃ are alkyl having from 1 to 6 carbons, not more than two of R₁, R₂and R₃ being substituted with a group selected from hydroxy; mono- orpolyhydroxyalkl having from 1 to 4 carbons and from 1 to 3 hydroxygroups; alkloxy, mono- or polyhydroxyalkyloxy having from 1 to 4 carbonsand from 0 to 3 hydroxy groups; amino or alkylamino having from 1 to 3carbons in the alkyl group; amidoalkyl having from 1 to 3 carbons; halo;cyano, or nitro, and R is hydrogen, methyl or ethyl.
 8. The compositionof claim 6 wherein R is hydrogen; R₄ is alkylene or amidoalkyl, and R₁,R₂, and R₃ are alkyl or monohydroxyalkyl.
 9. A method of coloring hairor treating skin which comprises contacting hair a skin with aneffective hair dyeing a skin treating amount of a polymer obtained byoxidatively polymerizing a compound of the formula: ##STR7## wherein: Yis --O-- or ##STR8## R is hydrogen or an akyl having 1 to 6 carbons, R₁,R₂, R₃ and R₄ are groups that in combination one with the otherquaternize the nitrogen to which they and R are bonded, andX is ananion.
 10. The method of claim 9 in which:R is hydrogen, methyl orethyl, R₄ is alkylene group of from 1 to 20 carbons; an amidoalkylgroup, the alkyl having from 1 to 6 carbons; an alkylene- ordialkylene-substituted aryl or alicyclic group, the alkylene group (s)having from 1 to 6 carbons, or a heterocyclic group selected frommorpholinyl, piperidinyl or pyrrole, and R₁, R₂ and R₃, which may be thesame or different, are alkyls of from 1 to 22 carbons, an alkylamidogroup, the alkyl having from 1 to 6 carbons; an alkyl- ordialkyl-substituted aryl or alicyclic group, the alkyl group(s) havingfrom 1 to 6 carbons or a heterocyclic group selected from morpholinyl,piperidinyl or pyrrole, each group R₁ , R₂, R₃ and R₄ beingunsubstituted or substituted with a substituent that does not preventester or amide formation, the substituents being selected from the groupconsisting of hydroxy; mono- and polyhydroxyalkl having from 1 to 4carbons and from 1 to 3 hydroxy groups; alkloxy, mono- andpolyhydroxyalkyloxy having from 1 to 4 carbons and from 0 to 3 hydroxygroups; amino and alkylamino having from 1 to 6 carbons in the alkylgroup; amidoalkyl having from 1 to 6 carbons; halo; cyano, and nitro.11. The method of claim 10 wherein R is an alkylene and has from 6 to 15carbons; at least two of R₁, R₂ or R₃ are alkyl having from 1 to 6carbons, not more than two of R₁, R₂ and R₃ being substituted withgroups consisting of hydroxy; mono- or polyhydroxyalkl having from 1 to2 carbons and from 1 to 2 hydroxy groups; alkloxy, mono- orpolyhydroxyalkyloxy having from 1 to 2 carbons or from 0 to 2 hydroxygroups; amino or alkylamino having from 1 to 3 carbons in the alkylgroup; amidoalkyl having from 1 to 3 carbons; halo; cyano, or nitro, andR is hydrogen.
 12. The method of claim 10 wherein R is hydrogen; R₄ isalkylene or amidoalkyl, and R₁, R₂, and R₃ are alkyl ormonohydroxyalkyl.